CN102557229B - Constant volume internal combustion type supercritical fluid oxidation device and oxidation method thereof - Google Patents
Constant volume internal combustion type supercritical fluid oxidation device and oxidation method thereof Download PDFInfo
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Abstract
The invention relates to a constant volume internal combustion type supercritical fluid oxidation device and an oxidation method thereof. According to the constant volume internal combustion type supercritical fluid oxidation device, a fuel input pipe and an oxidant input pipe penetrate through a reactor shell, an inorganic polymer and a reactor liner and is communicated with a reactor inner cavity; a discharge pipe and a safety valve are arranged on the lower part of a phase separator; and an upper thermometer, a lower thermometer and a pressure gauge are arranged in the reactor inner cavity. According to the constant volume internal combustion type supercritical fluid oxidation device, a reactor is heated and pressurized in a constant volume internal combustion mode, so that various reaction regulators are added easily, energy consumption is reduced, harmful organic matters are treated harmlessly, and the problems of quick corrosion of materials on the inner wall surface of the reactor, salt attachment to a reaction flow path and the inner wall of the reactor, high equipment cost and running cost and the like in the conventional supercritical water oxidation technology which cannot solve the problems are solved radically. Compared with the prior art, the constant volume internal combustion type supercritical fluid oxidation device has the advantages of simple structure of the reactor, wide treatment range, high efficiency, no secondary pollution, energy conservation, high possibility of separating inorganic salt and the like.
Description
Technical field:
The present invention relates to a kind of supercutical fluid oxide treatment harmful organic substances technology, especially the efficient generation of the mixture of supercritical water and supercritical co and use the method for this supercutical fluid oxide treatment harmful organic substances, specifically relate to the mode of internal combustion and come subcritical water in the heating and pressurizing constant volume container, oxygenant and harmful organic substance, make the temperature and pressure of these materials surpass stagnation point (temperature＞374 ℃ of water; Pressure＞22.1MPa).
Background technology:
Supercritical water oxidation (supercritical water oxidation, SCWO) technology is to process the very effective technology of liquid harmful organic substances.M.D.Bermejo and M.J.Cocero (Supercritical Water Oxidation:A Technical Review, AIChE is (2006) 3933-3951 J.52) to have summarized this technology and can efficiently process up hill and dale harmful organic substances (such as utmost point poisonous substance matter PCBs) and can reach 99.9999% at 60 seconds with interior rate of decomposition, this is that existing other treatment technologies are beyond one's reach.But, because common small intermittent-type (Batch system), such as Veriansyah Bambang, Kim Jae-duck (Supercritical water oxidation for the destruction of toxic organic wastewaters:A Review, J.of Environmental Sciences19 (2007) 512-522) described, such SCWO treatment system is to come the material in the heating container to make it the stagnation point that increasing temperature and pressure surpasses water by indirect heating constant volume reactor, and the oxygenant under the environment of supercritical water in the container and harmful organic substance reaction reach innoxious.This will ask the wall surface material of reactor namely will have the high heat transfer function to have again highly corrosion resistant, high withstand voltage function.
Philip A.Marrone, Glenn T.Hong (Review:Corrosion control methods in superitical water oxidation and gasification processes, J.of Supercritical Fluids 51 (2009) 83-103) explicitly points out does not also have a kind of material to have all these functions till now.In addition, the salt of organic oxidation generation can separate out to be attached on the reaction vessel can increase wall surface material corrosion and thermal conduction resistance.
In addition, continous way (Continuous flow system) SCWO treatment system is that habitual level pressure external heating mode (such as the SUWOX of Germany) or level pressure infiltration wall formula (Transpiring wall reactor, TWR) are to come the reacting by heating material with internal combustion such as B.Wellig et al. (Hydrothermal methanol diffusion flame as internal heat source in a SCWO reactor J.of Supercritical Fluids49 (2009) 59-70).All participate in reactive material (fuel, oxygenant, organic liquor, water etc.) in the lower pumping of overcritical pressure (being higher than 25MPa) but this must use a plurality of high energy consumption high-pressure pump, although available liquid oxidizer is (such as H
2O
2) directly join and reduce high-pressure pump in the organic liquor and use number, but this so that during heating organism and oxidant reaction to generate the price that salt is attached to minimizing pre-heat effect on the inwall of stream and the reactor wall and liquid oxidizer be very expensive (such as H
2O
2Price can be high and tens times of oxygen).These continuous reaction systems are the problem of separating out that prevents from adhering to of serious corrosion and salt from having used a large amount of pure water to separate product and reactor wall and increase the solubility control salt of salt with very high operating pressure, as S.Baur et al. (The destruction of industrial aqueous waste containing biocides in supercritical water:development of the SUWOX process for the technical application J.of Supercritical Fluids33 (2005) 149-157), are to have used operating pressure to be 70MPa.The price of high-pressure pump is that the maximum pumpage with high-pressure pump is similar to exponential relationship, and this is just so that existing supercritical water oxidation is processed the high cost of liquid harmful organic substances.Particularly the enforcement of large-scale is very difficult.
CN1730414 discloses " a kind of method of using supercritical water oxidation to process waste water ", is that waste water is forced into 22.1-30MPa, is preheated to 300-370 ℃; Under the condition that keeps uniform pressure, the input of the waste water after preheating desalination plant is warming up to 450-650 ℃ carries out desalination; To contain oxidant fluid and be forced into 22.1-30MPa, be warming up to 550-650 ℃, contain oxidant fluid by the oxygenant molar weight be the theoretical aerobic molar weight of organism complete oxidation 2-6 doubly with step (2) desalination after waste water be mixed into the supercritical reaction device, the control temperature is 550-650 ℃, pressure is 22.1-30MPa, the residence time is 10-40 second, carries out supercritical water oxidation.
CN101182065 discloses " method that a kind of high-concentration organic waste water in acroleic acid production is processed " (1) and oxygenant and deionized water has been hybridly prepared into oxidizing agent solution, and places in the oxygenant tank; (2) acrylic acid production waste water and clear water are placed respectively in waste water and the clean water tank, and in waste water, add catalyzer; (3) at first preheater is heated to 300-400 ℃, reactor is heated to 400-600 ℃; (4) opening high pressure ram pump sample introduction, waste water and oxidizing agent solution enter in the reactor micropore ceramic tube after preheating, pressurization respectively, carry out supercritical water oxidation under 374 ℃-600 ℃ of pressure 22-28MPa and temperature, clear water is by in the ceramic membrane outer wall infiltration into microporous vitrified pipe; (5) process water outlet and after cooling and gas-liquid separation, can realize qualified discharge.
CN101928080A disclose " a kind of supercritical water oxidation treatment method of high concentrated organic wastewater " comprise boost, the process such as preheating, supercritical water oxidation.Content by chlorion and salt in the restriction waste water stops up equipment corrosion and pipeline and is controlled in the scope that can bear; The COD concentration of control waste water makes oxidizing reaction reach reaction self-heating.
Above-mentioned existing technology all is to move under high-temperature and high-pressure conditions, and treatment facility is difficult to maximize.During low PH, under the condition that especially chlorion exists, equipment corrosion is serious, and general material is difficult to satisfy equipment requirements.Salt in the supercritical water oxidation process in the equipment is almost all separated out, and easily causes the obstruction of pipeline, causes equipment to move continuously.
Summary of the invention:
Purpose of the present invention just is to provide a kind of constant volume internal combustion type supercritical fluid oxidation device for above-mentioned the deficiencies in the prior art;
Another object of the present invention just is to provide a kind of method for oxidation of constant volume internal combustion type supercritical fluid oxidation device.
The objective of the invention is to be achieved through the following technical solutions:
Constant volume internal combustion type supercritical fluid oxidation device, be to pass shell of reactor 14, geopolymer 15 and reactor inner container 17 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3 to communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14; Oxygenant input tube 4 passes shell of reactor 14, inorganic polymer 15 and reactor inner container 17 through oxygenant transfer valve 5 and communicates with reactor inner chamber 12, and is welded and fixed with reactor inner container 17 and shell of reactor 14; Organic liquid waste input tube 10 passes shell of reactor 14, geopolymer 15 and reactor inner container 17 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8 and communicates with reactor inner chamber 12, and is welded and fixed with reactor inner container 17 and shell of reactor 14; The top of phase separator 24 is passed shell of reactor 14, geopolymer 15 and reactor inner container 17 by pipeline through reactant outlet valve 18 or safety valve 19 respectively and is communicated with reactor inner chamber 12 bottoms, and is welded and fixed with reactor inner container 17 and shell of reactor 14; Outlet valve 25 and vent pipe 26 are equipped with in the bottom of phase separator 24; The upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 by pipeline, gas-liquid separator 22 tops are provided with gas outlet pipe 21, gas-liquid separator 22 bottoms are provided with liquid discharge tube 23, upper temp meter 11 is equipped with on reactor inner chamber 12 tops, temperature of lower meter 13 is equipped with in reactor inner chamber 12 bottoms, and reactor inner chamber 12 middle parts are equipped with pressure warning unit 16 and are consisted of.
Fuel inlet pipe 1 in fuel transfer valve 3 bottoms is equipped with fuel heater 6, at the front end of organic liquid waste transfer valve 8 organic liquid waste well heater 7 is housed.
Fuel heater 6 and organic liquid waste well heater 7 are solar heater or electric heater.
Between reactor inner container 17 and the shell of reactor 14 apart from 0.3--10cm, filling geopolymer 15 between reactor inner container 17 and the shell of reactor 14, geopolymer (Geopolymer) 15 can be made of a series of inorganic polymer, usually can be by alukalin (metakaolin), the fine grinding water-granulated slag, flyash, alkali (KOH), sodium silicate and water form, with the above-mentioned materials mixing of weighing by a certain percentage, be poured between reactor inner container 17 and the shell of reactor 14 after being stirred into slurry, form high temperature resistant through the maintenance sclerosis, high pressure resistant, anticorrosive and have good heat-proof quality material.The pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively.The geopolymer proportioning by weight ratio that the present invention selects is: alukalin: fine mill slag: alkali: sodium silicate: water=80: 10: 6: 17: 21; Or fine mill slag: alkali: sodium silicate: water=125: 8: 21: 52; Or fine mill slag: flyash: alkali: sodium silicate: water=150: 100: 16: 43: 53, alkali is will be in advance water-soluble to be re-used after making solution.
The preferred KOH of described alkali, NaOH, K
2CO
3Or Na
2CO
3
The starting material that adopt are: I level flyash, slag are the S105 levels, and the modulus of water glass is 2.8.
The method for oxidation of constant volume internal combustion type supercritical fluid oxidation device comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and safety valve 19, after reactor inner chamber 12 injects the 0.3-0.5MPa oxygenant, close oxygenant transfer valve 5 by oxygenant input tube 4 and oxygenant transfer valve 5, stop oxygenant and inject;
B, open organic liquid waste transfer valve 8, inject organic liquid waste by organic liquid waste input tube 10 and high pressure organic liquid waste volume pump 9 to reactor inner chamber 12, when the pressure of reactor inner chamber (12) reaches 5-8MPa, close high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8, stop organic liquid waste and inject; , heat to organic liquid waste by organic liquid waste well heater 7 to the process that reactor inner chamber 12 injects at organic liquid waste;
D, open fuel transfer valve 3, inject fuel by fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor inner chamber 12, in the process of fuel to 12 injections of reactor inner chamber, be heated to above 500 ℃ by well heater 6 to fuel, inject fuel spontaneous ignition under the help of oxygenant of reaction vessel inner chamber 12;
E, monitor the response behaviour of the material in the reactor inner chambers 12 by upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16, temperature in reactor inner chamber 12, pressure have surpassed the stagnation point of water, to be upper temp meter 11 with the temperature of temperature of lower meter 13 all reach is higher than 500 ℃, when reaching 30MPa-40MPa, the pressure of pressure warning unit 16 closes fuel under high pressure volume pump 2 and fuel transfer valve 3, stop fuel feed, kept 30 seconds;
F, then open the safety-valve 19, give the reactor inner chamber 12 decompressions, when the pressure of reactor inner chamber 12 drops to 20MPa closed safe valve 19 when following, open reactant outlet valve 18, allow the material in the reactor inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
G, open reducing valve 20 fluids and enter gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
H, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.3%.
Described oxygenant is oxygen.
Described fuel is methanol aqueous solution (28wt%CH
3OH+72wt%H
2O) self-ignition temperature of fuel is less than 500 ℃.
The benefit effect: the present invention supplies with organic liquor to constant volume reactor oxygen gas-supplying with at the low pressure downhill reaction device of 2.0-5.0MPa under the low pressure of 0.3-0.5MPa, fuel is pumped in the reaction vessel and the oxygen mix burning with high pressure measurement, makes material in the reactor surpass stagnation point (temperature＞374 ℃ of water; Pressure＞22.1MPa).The energy consumption of material from the subcritical state to the supercritical state obtains decrease in the reactor, and this is so that the running cost of device obtains decrease.Reactor inner container 17 of the present invention adopts the alloy625 steel alloy of heat-and corrosion-resistant, geopolymer 15 is heat insulation transmission of pressure material, shell of reactor 14 adopts the SS316 stainless steel, satisfy high temperature resistant, corrosion-resistant, heat insulation and high voltage bearing requirement, simultaneously also so that the manufacturing cost of device reduce significantly.Because reactor is the constant volume internal combustion type heating and pressurizing, even there is the salt of separating out can not produce large impact to rate of heating in adhering to also of inner-wall surface.Various reaction adjusting agents are easily added in the easy mass-producing of such reactor.This is that existing supercritical water oxidation treatment technology is not available.Use energy consumption of the present invention low, efficient is high, thoroughly harmless treatment harmful organic substances.Solved three problems in the existing supercritical Water Oxidation Technology: the corrosion of (1) reactor wall plane materiel material is too fast; (2) reaction stream and reactor wall salt adheres to; (3) the too high problem of equipment cost and running cost.Compared with prior art, the present invention has the advantages such as structure of reactor is simple, and process range is wide, and efficient is high, and non-secondary pollution is saved the energy, and inorganic salt are easily separated.
Description of drawings:
Accompanying drawing is the constant volume internal combustion type supercritical fluid oxidation device structure iron
1 fuel inlet pipe, 2 petrolifts, 3 fuel transfer valves, 4 oxygenant input tubes, 5 oxygenant transfer valves, 6 fuel heaters, 7 organic liquid waste well heaters, 8 organic liquid waste transfer valves, 9 organic liquid waste front pumps, 10 organic liquid waste input tubes, 11 upper temp meters, 12 reactor inner chambers, 13 temperature of lower meters, 14 shell of reactor, 15 inorganic polymers, 16 pressure warning units, 17 reactor inner container, 18 reactant outlet valves, 19 safety valve, 20 reducing valve, 21 gas outlet pipes, 22 vapour liquid separators, 23 liquid discharge tubes, 24 phase separators, 25 outlet valves, 26 vent pipes
Embodiment:
Be described in further detail below in conjunction with drawings and Examples:
Embodiment 1
Constant volume internal combustion type supercritical fluid oxidation device, to pass shell of reactor 14 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, oxygenant input tube 4 passes shell of reactor 14 through oxygenant transfer valve 5, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, organic liquid waste input tube 10 passes shell of reactor 14 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, the top of phase separator 24 is passed shell of reactor 14 by pipeline through reactant outlet valve 18 and safety valve 19 respectively, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12 bottoms, and be welded and fixed with reactor inner container 17 and shell of reactor 14, vent pipe 26 and outlet valve 25 are equipped with in the bottom of phase separator 24, the upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 by pipeline, gas-liquid separator 22 tops are provided with gas outlet pipe 21, gas-liquid separator 22 bottoms are provided with liquid discharge tube 23, in the reactor, upper temp meter 11 is equipped with on 12 tops, and upper temp meter 11 links to each other with reactor is outside by the outer wall of wire along oxygenant input tube 4; Temperature of lower meter 13 is equipped with in reactor inner chamber 12 bottoms, and temperature of lower meter 13 links to each other with reactor is outside by the outer wall of wire along the reactant vent pipe; Pressure warning unit 16 is equipped with at reactor inner chamber 12 middle parts, and pressure warning unit 16 is by the outer wall and reactor outside link to each other formation of wire along organic liquid waste input tube 10.
Fuel inlet pipe 1 in fuel transfer valve 3 bottoms is equipped with fuel heater 6, at the front end of organic liquid waste transfer valve 8 organic liquid waste well heater 7 is housed.Fuel heater 6 and organic liquid waste well heater 7 are electric heater.Reactor inner container 17 adopts the alloy625 steel alloy of heat-and corrosion-resistant, and shell of reactor 14 adopts the SS316 stainless steel.Between reactor inner container 17 and the shell of reactor 14 apart from 2cm, the geopolymer Geopolymer between reactor inner container 17 and the shell of reactor 14) be to be mixed by 800g alukalin, 200g fine mill slag, 60gKOH, 170g sodium silicate, 210g water to consist of; Through being stirred into the slurry after-pouring between reactor inner container 17 and the shell of reactor 14, form high temperature resistant, high pressure resistant, anticorrosive and have the inorganic materials of good heat-proof quality through maintenance sclerosis, the pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively, after tested, ultimate compression strength is 65MPa.In advance KOH is made the aqueous solution re-uses.
The method for oxidation of constant volume internal combustion type supercritical fluid oxidation device comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and safety valve 19, inject the oxygen of 0.5MPa to reactor inner chamber 12 by oxygenant input tube 4 and oxygenant transfer valve 5, after close oxygenant transfer valve 5, stop oxygen and inject; Safety valve 19 operating pressure are 60MPa;
B, open organic liquid waste transfer valve 8, be the phenol organic liquid waste of 1wt.% to reactor inner chamber 12 implantation concentrations by organic liquid waste input tube 10 and high pressure organic liquid waste volume pump 9, when reaching 5MPa, the pressure of reactor inner chamber (12) closes organic liquid waste transfer valve 8, stop the organic liquid waste input, to the process that input reactor inner chamber 12 injects, be heated to 350 ℃ by organic liquid waste well heater 7 to organic liquid waste at organic liquid waste; High pressure organic liquid waste volume pump (NP-KX-720: peak pressure 10MPa; 0.2-200ml/min)
C, open fuel transfer valve 3, inject methanol aqueous solution by fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor inner chamber 12, inject the process of methanol aqueous solution to reactor inner chamber 12 at fuel under high pressure volume pump 2, be heated to above 500 ℃ by well heater 6 to methanol aqueous solution, inject methanol aqueous solution spontaneous ignition burning under the help of oxygen of reaction vessel inner chamber 12; Fuel under high pressure volume pump 2 (NP-KX-520: maximum 60MPa; 0.2-20ml/min)
D, monitor the response behaviour of the material in the reactor inner chambers 12 by upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16, temperature, pressure in reactor inner chamber 12 has surpassed the stagnation point of water, the temperature that is upper temp meter 11 and temperature of lower meter 13 all is higher than 500 ℃, the pressure of pressure warning unit 16 is closed fuel under high pressure volume pump 2 and fuel transfer valve 3 after being higher than 30MPa, stop methanol aqueous solution and supply with, kept 30 seconds;
E, then open the safety-valve 19, give the reactor inner chamber 12 decompressions, when the pressure of reactor inner chamber 12 drops to 20MPa closed safe valve 19 when following, open reactant outlet valve 18, allow the material in the reactor inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
F, open reducing valve 20 fluids and enter gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
G, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.5%.
Embodiment 2
Constant volume internal combustion type supercritical fluid oxidation device, to pass shell of reactor 14 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, oxygenant input tube 4 passes shell of reactor 14 through oxygenant transfer valve 5, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, organic liquid waste input tube 10 passes shell of reactor 14 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, the top of phase separator 24 is passed shell of reactor 14 by pipeline through reactant outlet valve 18 and safety valve 19 respectively, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12 bottoms, and be welded and fixed with reactor inner container 17 and shell of reactor 14, vent pipe 26 and outlet valve 25 are equipped with in the bottom of phase separator 24, the upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 by pipeline, gas-liquid separator 22 tops are provided with gas outlet pipe 21, gas-liquid separator 22 bottoms are provided with liquid discharge tube 23, in the reactor, upper temp meter 11 is equipped with on 12 tops, and upper temp meter 11 links to each other with reactor is outside by the outer wall of wire along oxygenant input tube 4; Temperature of lower meter 13 is equipped with in reactor inner chamber 12 bottoms, and temperature of lower meter 13 links to each other with reactor is outside by the outer wall of wire along the reactant vent pipe; Pressure warning unit 16 is equipped with at reactor inner chamber 12 middle parts, and pressure warning unit 16 is by the outer wall and reactor outside link to each other formation of wire along organic liquid waste input tube 10.
Fuel inlet pipe 1 in fuel transfer valve 3 bottoms is equipped with fuel heater 6, at the front end of organic liquid waste transfer valve 8 organic liquid waste well heater 7 is housed.Fuel heater 6 and organic liquid waste well heater 7 are electric heater.Reactor inner container 17 adopts the alloy625 steel alloy of heat-and corrosion-resistant, and shell of reactor 14 adopts the SS316 stainless steel.
Between reactor inner container 17 and the shell of reactor 14 apart from 4.0cm, the geopolymer (Geopolymer) between reactor inner container 17 and the shell of reactor 14 is by 1000g fine mill slag, 162g K
2CO
3, 210g water and 168g sodium silicate mix and consist of; Through being stirred into the slurry after-pouring between reactor inner container 17 and the shell of reactor 14, form high temperature resistant, high pressure resistant, anticorrosive and have the inorganic materials of good heat-proof quality through maintenance sclerosis, the pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively, ultimate compression strength is 90MPa after tested.K
2CO
3The solution of making soluble in water re-uses in advance.
The method for oxidation of constant volume internal combustion type supercritical fluid oxidation device comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and safety valve 19, inject 0.4MPa oxygen by oxygenant input tube 4 and oxygenant transfer valve 5 to reactor inner chamber 12, after close oxygenant transfer valve 5, stop oxygen and inject; Safety valve 19 operating pressure are 60MPa;
B, open organic liquid waste transfer valve 8, be acetone (acetone) organic liquid waste of 1wt.% to reactor inner chamber 12 implantation concentrations by organic liquid waste input tube 10 and high pressure organic liquid waste volume pump 9, when reaching 6MPa, the pressure of reactor inner chamber (12) closes organic liquid waste transfer valve 8, stop the organic liquid waste input, to the process that input reactor inner chamber 12 injects, be heated to 350 ℃ by organic liquid waste well heater 7 to organic liquid waste at organic liquid waste;
C, open fuel transfer valve 3, inject methanol aqueous solution by fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor inner chamber 12, inject the process of methanol aqueous solution to reactor inner chamber 12 at fuel under high pressure volume pump 2, be heated to above 500 ℃ by well heater 6 to methanol aqueous solution, spray into the methanol aqueous solution spontaneous ignition burning under the help of oxygenant in the reaction vessel inner chamber 12;
D, monitor the response behaviour of the material in the reactor inner chambers 12 by upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16, temperature, pressure in reactor inner chamber 12 has surpassed the stagnation point of water, to be upper temp meter 11 with the temperature of temperature of lower meter 13 reach is higher than 500 ℃, the pressure of pressure warning unit 16 is closed fuel under high pressure volume pump 2 and fuel transfer valve 3 after being higher than 30MPa, stop methanol aqueous solution and supply with, kept 30 seconds;
E, then open the safety-valve 19, give the reactor inner chamber 12 decompressions, when the pressure of reactor inner chamber 12 drops to 20MPa closed safe valve 19 when following, open reactant outlet valve 18, allow the material in the reactor inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
F, open reducing valve 20 fluids and enter gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
G, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.8%.
Embodiment 3
Constant volume internal combustion type supercritical fluid oxidation device, to pass shell of reactor 14 by fuel inlet pipe 1 through fuel under high pressure volume pump 2 and fuel transfer valve 3, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, oxygenant input tube 4 passes shell of reactor 14 through oxygenant transfer valve 5, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, organic liquid waste input tube 10 passes shell of reactor 14 through high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12, and be welded and fixed with reactor inner container 17 and shell of reactor 14, the top of phase separator 24 is passed shell of reactor 14 by pipeline through reactant outlet valve 18 and safety valve 19 respectively, geopolymer 15 and reactor inner container 17 communicate with reactor inner chamber 12 bottoms, and be welded and fixed with reactor inner container 17 and shell of reactor 14, vent pipe 26 and outlet valve 25 are equipped with in the bottom of phase separator 24, the upper side of phase separator 24 links to each other with gas-liquid separator 22 with reducing valve 20 by pipeline, gas-liquid separator 22 tops are provided with gas outlet pipe 21, gas-liquid separator 22 bottoms are provided with liquid discharge tube 23, in the reactor, upper temp meter 11 is equipped with on 12 tops, and upper temp meter 11 links to each other with reactor is outside by the outer wall of wire along oxygenant input tube 4; Temperature of lower meter 13 is equipped with in reactor inner chamber 12 bottoms, and temperature of lower meter 13 links to each other with reactor is outside by the outer wall of wire along the reactant vent pipe; Pressure warning unit 16 is equipped with at reactor inner chamber 12 middle parts, and pressure warning unit 16 is by the outer wall and reactor outside link to each other formation of wire along organic liquid waste input tube 10.
Fuel inlet pipe 1 in fuel transfer valve 3 bottoms is equipped with fuel heater 6, at the front end of organic liquid waste transfer valve 8 organic liquid waste well heater 7 is housed.Fuel heater 6 and organic liquid waste well heater 7 are the solar heat device.Reactor inner container 17 adopts the alloy625 steel alloy of heat-and corrosion-resistant, and shell of reactor 14 adopts the SS316 stainless steel.
Between reactor inner container 17 and the shell of reactor 14 apart from 6.0cm, the geopolymer Geopolymer between reactor inner container 17 and the shell of reactor 14) be to be mixed by 600g fine mill slag, 400g flyash, 45gNaOH, 172g sodium silicate and 212g water to consist of; Through being stirred into the slurry after-pouring between reactor inner container 17 and the shell of reactor 14, form high temperature resistant, high pressure resistant, anticorrosive and have the inorganic materials of good heat-proof quality through maintenance sclerosis, the pressure that reactor inner container 17 is born passes to shell of reactor 14 effectively, and ultimate compression strength is 73Mpa after tested.In advance NaOH is made the aqueous solution re-uses.
The method for oxidation of constant volume internal combustion type supercritical fluid oxidation device comprises following order and step:
A, at first close fuel transfer valve 3, organic liquid waste transfer valve 8, reactant outlet valve 18 and safety valve 19, after reactor inner chamber 12 injects 0.3MPa oxygen, close oxygenant transfer valve 5 by oxygenant input tube 4 and oxygenant transfer valve 5, stop oxygen and inject;
B, open organic liquid waste transfer valve 8, by organic liquid waste input tube 10 and high pressure organic liquid waste volume pump 9 chlorophenesic acid to reactor inner chamber 12 implantation concentration 1wt.% (2-chlorphenol), adhere at the reactor wall face for accelerated reaction and control corrosion and generation salt, add 50mg Na by the 1kg organic liquid waste
2CO
3Be metered into Na
2CO
3In reactor inner chamber 12, when reaching 7MPa, the pressure of reactor inner chamber 12 closes high pressure organic liquid waste volume pump 9 and organic liquid waste transfer valve 8, stop the organic liquid waste input, to the process that input reactor inner chamber 12 injects, be heated to 350 ℃ by organic liquid waste well heater 7 to organic liquid waste at organic liquid waste;
C, open fuel transfer valve 3, inject methanol aqueous solutions by fuel inlet pipe 1 and fuel under high pressure volume pump 2 to reactor inner chamber 12, self-ignition temperature is less than 500 ℃.To the process that reactor inner chamber 12 injects, be heated to above 500 ℃ by well heater 6 to methanol aqueous solution at methanol aqueous solution, spray into the methanol aqueous solution spontaneous ignition burning under the help of oxygenant in the reaction vessel inner chamber 12;
D, monitor the response behaviour of the material in the reactor inner chambers 12 by upper temp meter 11, temperature of lower meter 13 and pressure warning unit 16, temperature, pressure in reactor inner chamber 12 has surpassed the stagnation point of water, to be upper temp meter 11 with the temperature of temperature of lower meter 13 reach is higher than 500 ℃, the pressure of pressure warning unit 16 is closed fuel under high pressure volume pump 2 and fuel transfer valve 3 after surpassing 35MPa, stop fuel feed, kept 30 seconds;
E, then open the safety-valve 19, give the reactor inner chamber 12 decompressions, when the pressure of reactor inner chamber 12 drops to 20MPa closed safe valve 19 when following, open reactant outlet valve 18, allow the material in the reactor inner chamber 12 spray into phase separator 24, make solid salt and fluid separation;
F, open reducing valve 20 fluids and enter gas-liquid separator 22, gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe 21
2O discharges through liquid discharge tube 23;
G, open outlet valve 25 at last, contain saline solution and discharge through vent pipe 26, use TOC (Total organic carbon) analysis meter (Sievers InnovOx Lab) to measure discharge opeing, the TOC transformation efficiency is higher than 99.9%.
Claims (7)
1. constant volume internal combustion type supercritical fluid oxidation device, by the bottom of phase separator (24) vent pipe (26) and outlet valve (25) to be housed, the upper portion side wall of phase separator (24) links to each other with vapour liquid separator (22) with reducing valve (20) by pipeline, vapour liquid separator (22) top is provided with gas outlet pipe (21), vapour liquid separator (22) bottom is provided with liquid discharge tube (23), upper temp meter (11) is equipped with on reactor inner chamber (12) top, temperature of lower meter (13) is equipped with in reactor inner chamber (12) bottom, reactor inner chamber (12) middle part is equipped with pressure warning unit (16) and is formed, it is characterized in that, to pass shell of reactor (14) by fuel inlet pipe (1) through fuel under high pressure volume pump (2) and fuel transfer valve (3), geopolymer (15) and reactor inner container (17) communicate with reactor inner chamber (12), and be welded and fixed with reactor inner container (17) and shell of reactor (14), oxygenant input tube (4) passes shell of reactor (14) through oxygenant transfer valve (5), geopolymer (15) and reactor inner container (17) communicate with reactor inner chamber (12), and be welded and fixed with reactor inner container (17) and shell of reactor (14), organic liquid waste input tube (10) passes shell of reactor (14) through high pressure organic liquid waste volume pump (9) and organic liquid waste transfer valve (8), geopolymer (15) and reactor inner container (17) communicate with reactor inner chamber (12), and be welded and fixed with reactor inner container (17) and shell of reactor (14), the top of phase separator (24) is passed shell of reactor (14) by pipeline through reactant outlet valve (18) or safety valve (19) respectively, geopolymer (15) and reactor inner container (17) communicate with reactor inner chamber (12) bottom, and are welded and fixed formation with reactor inner container (17) and shell of reactor (14).
2. according to constant volume internal combustion type supercritical fluid oxidation device claimed in claim 1, it is characterized in that, fuel inlet pipe (1) in the bottom of fuel transfer valve (3) is equipped with fuel heater (6), at the front end of organic liquid waste transfer valve (8) organic liquid waste well heater (7) is housed.
3. according to constant volume internal combustion type supercritical fluid oxidation device claimed in claim 2, it is characterized in that, fuel heater (6) and organic liquid waste well heater (7) are solar heater or electric heater.
4. according to constant volume internal combustion type supercritical fluid oxidation device claimed in claim 1, it is characterized in that, distance between reactor inner container (17) and the shell of reactor (14) is 0.3--10cm, filling geopolymer (15) therebetween, geopolymer (15) proportioning by weight ratio is: alukalin: fine mill slag: KOH: sodium silicate: water=80:10:6:17:21; Or fine mill slag: K
2CO
3: sodium silicate: water=500:81:105:84; Or fine mill slag: flyash: NaOH: sodium silicate: water=600:400:45:172:212, alkali are will be in advance water-soluble to be re-used after making solution.
5. according to constant volume internal combustion type supercritical fluid oxidation device claimed in claim 4, it is characterized in that the preferred KOH of described alkali, NaOH, K
2CO
3Or Na
2CO
3
6. the method for oxidation of a constant volume internal combustion type supercritical fluid oxidation device is characterized in that, comprises following order and step:
A, at first close fuel transfer valve (3), organic liquid waste transfer valve (8), reactant outlet valve (18) and safety valve (19), inject the 0.3-0.5MPa oxygenant by oxygenant input tube (4) and oxygenant transfer valve (5) to reactor inner chamber (12), after close oxygenant transfer valve (5), stop oxygenant and inject;
B, open organic liquid waste transfer valve (8), inject organic liquid waste by organic liquid waste input tube (10) and high pressure organic liquid waste volume pump (9) to reactor inner chamber (12), when reaching 5-8MPa, the pressure of reactor inner chamber (12) closes organic liquid waste transfer valve (8), stop the organic liquid waste input,, heat to organic liquid waste by organic liquid waste well heater (7) to the process that reactor inner chamber (12) injects at organic liquid waste;
C, open fuel transfer valve (3), inject fuel by fuel inlet pipe (1) and fuel under high pressure volume pump (2) to reactor inner chamber (12), in the process of fuel to reactor inner chamber (12) injection, be heated to above 500 ℃ by well heater (6) to fuel, spray into the fuel spontaneous ignition burning under the help of oxygenant in the reaction vessel inner chamber (12);
D, monitor the response behaviour of the material in the reactor inner chamber (12) by upper temp meter (11), temperature of lower meter (13) and pressure warning unit (16), temperature, pressure in reactor inner chamber (12) has surpassed the stagnation point of water, to be upper temp meter (11) with the temperature of temperature of lower meter (13) reach is higher than 500 ℃, when reaching 30MPa-40MPa, the pressure of pressure warning unit (16) closes fuel transfer valve (3), stop fuel feed, kept 20 seconds;
E, (19) then open the safety-valve, give reactor inner chamber (12) decompression, when the pressure of reactor inner chamber (12) drops to 20MPa closed safe valve (19) when following, open reactant outlet valve (18), allow the material in the reactor inner chamber (12) spray into phase separator (24), make solid salt and fluid separation;
F, open reducing valve (20) fluid and enter gas-liquid separator (22), gas-liquid separation under normal pressure, gas CO
2, O
2Discharge liquid H through gas outlet pipe (21)
2O discharges through liquid discharge tube (23);
G, open outlet valve (25) at last, contain saline solution and discharge through vent pipe (26), fuel transforms (Total organic carbon (TOC)) and is higher than 99.95%.
7. according to the method for oxidation of constant volume internal combustion type supercritical fluid oxidation device claimed in claim 6, it is characterized in that, described oxygenant is oxygen or H
2O
2
8. according to the method for oxidation of constant volume internal combustion type supercritical fluid oxidation device claimed in claim 6, it is characterized in that, described fuel is methanol aqueous solution (28wt%CH
3OH+72wt%H
2O), the self-ignition temperature of fuel is less than 500 ℃.
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| CN103512034B (en) * | 2013-09-30 | 2016-01-20 | 西安交通大学 | The overcritical hydro-thermal combustion reactor of organic wastewater |
| CN104907002A (en) * | 2015-06-09 | 2015-09-16 | 王冰 | Supercritical reaction kettle capable of sorting and discharging products automatically and method |
| KR101803875B1 (en) * | 2016-08-01 | 2017-12-04 | 엘지전자 주식회사 | Sterilizing water generation apparatus |
| CN108317540B (en) * | 2018-02-23 | 2020-06-09 | 新奥环保技术有限公司 | Supercritical water oxidation ignition system and ignition process |
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